Magnesiation of Phenol Derivatives Catalyzed by a Rhodium─Aluminum Complex

ABSTRACT Here we describe the generation of aryl Grignard reagents from phenol derivatives via C─O bond activation cooperatively catalyzed by Rh─Al heterobimetallic complexes. We discovered that the electron‐rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π‐extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.